Adhesive agent for application on a sanitary object

ABSTRACT

An agent for the sanitary sector, which agent can be applied directly on a sanitary object, adheres there and can be flushed away only after a relatively large number of flushing operations. The agent includes fillers from the group of surfactants and also an adhesion promoter. The adhesion promoter is selected from hydrogenated polystyrene derivatives and olefin homopolymers and copolymers of two or more olefins, where the olefin homopolymers and copolymers may also be partially hydrogenated, and the viscosity of the agent is at least 30 Pas, measured using a Haake viscometer, plate/plate system, plate diameter 10 mm, at a shear gradient of 2.62 s −1  and 20° C. and the agent is so sticky that it can serve to attach bar-shaped agents in the toilet bowl, wherein the concentration of the surfactants in the case of an adhesion promoter from the group of polyalkyleneimines is between 7 and 60% by weight.

The present application is a continuation-in-part of U.S. patentapplication Ser. No. 12/735,987, inventors Joachim Leipold et al., filedAug. 30, 2010, which in turn is a 371 of PCT Application No.PCT/EP2009/000873, filed Feb. 9, 2009, both of which are incorporatedherein by reference.

The present invention relates to an adhesive agent for the sanitarysector, which serves in particular for application on a sanitary objectsuch as a toilet bowl.

These agents are viscous, generally pasty agents, which are applieddirectly to the surface of the sanitary object from a suitablecontainer, adhere there and can be flushed away only after a relativelylarge number of flushing operations.

WO 99/66017 discloses adhesive sanitary agents which serve for cleaningand deodorization and comprise surfactants, water, fragrances andadhesion promoters. Following direct application on the sanitary object,these sanitary agents are flushed away only after a relatively largenumber of flush cycles.

A further development of these adhesive sanitary agents with smoothersurfaces as a consequence of additions of polyhydric alcohols isdisclosed in EP 1 325 103 B1.

Further adhesive sanitary agents based on block copolymers comprisingoligo- or polyalkylene oxides or on aryl ethoxylates or alkyl arylethoxylates as adhesion promoters are described in EP 1 318 191 B1 andadhesive sanitary agents containing bleaches are described in DE 10 2004056 554 A1.

The known adhesive sanitary agents can be applied in a simple andhygienic manner using a suitable device, they adhere to the surface ofthe sanitary object, retain their shape and are not flushed away intheir entirety even under the effect of water, but only graduallydissolve completely after a large number of flushes.

The particular advantage of these adhesive sanitary agents consists inthe fact that additional containers such as the so-called “WC cages”,the use of which is perceived by the consumer as being unhygienic,particularly when replacing the sanitary agent and when cleaning thetoilet, are avoided.

In the field of conventional bar-shaped toilet cleaning anddeodorization agents which are used in WC cages in the toilet bowl, inrecent years a large number of multiphase products has been supplied:

Thus, for example, agents with an additional bleach phase are describedin WO 00/23558, agents with a cleaning agent shaped-body phase and a gelphase are described in EP 1 418 225 A1 and cleaning agent shaped bodieswith one phase comprising water-soluble salts and one phase comprisingwater-insoluble salts are described in WO 00/58434.

As a result of dividing the various functions to be fulfilled by atoilet cleaning and deodorization agent between several phases, forexample a specific phase for intense deodorization and a special phaseexclusively for cleaning, such multiphase agents are able to better meetthe requirements of the consumer.

The object of the present invention is to provide a sanitary agent whichcan be applied in a simple and hygienic manner, which can be used indiverse ways and which fulfils consumer wishes with regard to intensedeodorization and good cleaning.

This object is achieved by the features of claim 1.

Surprisingly, it has been established that an agent with a viscosity ofat least 30 Pas, measured using a Haake viscometer, plate/plate system,plate diameter 10 mm, at a shear gradient of 2.62 s⁻¹ and 20° C., whichcomprises fillers and also an adhesion promoter, where the adhesionpromoter is selected from the group of hydrogenated polystyrenederivatives, olefin homopolymers and copolymers of two or more olefins,where the olefin homopolymers and copolymers may also be partiallyhydrogenated, can be applied not only directly on the sanitary object,adheres there and can be flushed away only after a relatively largenumber of flushing operations, but, as a consequence of its stickiness,can also serve to attach bar-shaped agents to the toilet bowl.

The special adhesion promoters mean that the agent adheres to thesanitary surface and that further materials such as bar-shaped agents,for example with cleaning or deodorizing active ingredients, can bestuck to the surface of the adhesive. Moreover, these adhesion promotersare characterized in that the agents comprising these adhesion promoterscan be flushed away without residue and that the agents comprising theseadhesion promoters are insensitive towards fluctuations in the mixingratio of adhesion promoter to filler.

By adding suitable fillers it is possible, for example, to adjust theviscosity and/or the flushability of the agent and to achieve thedesired deodorization or coloring of the agent.

A broader field of use is opened up by the agent according to theinvention:

In the application of the agent as “pure adhesive”, the agent serves asreplacement for the WC cages perceived as unhygienic by the consumer. Onthe adhesive applied to the toilet bowl surface it is possible to attachbar-shaped agents comprising active ingredients having their ownfunctionalities such as conventional rim blocks with one or more phases,rim blocks with scented phase, deodorization tablets, rim blockscontaining bleach etc., where the adhesive replaces the WC cage in anhygienic manner and is gradually flushed away by the stream of flushwater together with the bar-shaped agent adhering thereto. It is ofcourse also possible for tablets compacted from powders or granules orelse water-soluble or water-insoluble plastics containing activeingredients to be attached to the adhesive.

In this application, the agent has at least one of the adhesionpromoters according to the invention and a thickener. Since the adhesionpromoters according to the invention are generally viscous liquids, theaddition of a thickener as filler is required so that the agent has thedesired high viscosity of at least 30 Pas.

Further constituents such as dyes, fragrances, optionally surfactants,foamers etc. can of course also be added to this basic formulation ofadhesion promoter and thickener.

In one modification of the first embodiment, besides the adhesionpromoter and the thickener, the agent also has perfume so that it can beused simultaneously for adhesion and for deodorization.

In the second application, the adhesive has the adhesion promotersaccording to the invention and, as filler, surfactants, meaning that itcan itself take on the cleaning function as a result of the suitableselection of the type and concentration of the surfactants andoptionally further additives. The adhesive effect facilitates the fixingof further desired active ingredients in the toilet bowl, e.g. of afragrance, of a bleaching tablet, of a descaling tablet, of anadvertizing medium etc.

With the cleaning adhesive, the consumer can thus, for example, select ascent corresponding to his current wishes and press the correspondingdeodorization tablet onto the applied cleaning adhesive such that itsticks firmly to the adhesive, for example in order to deodorize thetoilet for the next 1 or 2 weeks.

The adhesive according to the invention thus even makes it possible tooffer the adhesive together with a series of deodorization tablets ordeodorization gels, bleaching tablets, descaling tablets, intensivecleaning tablets etc. in a combined set and thus to make it possible forthe user to individually equip the adhesive.

If the consumer would like additional bleaching, then, for example, ableaching tablet is stuck onto the surface of the adhesive.

If the consumer would like particularly powerful and intensive cleaningof the toilet, then another cleaning tablet can additionally be stuckonto the cleaning adhesive. The build-up of multilayered agentsconsisting of the layers adhesive-functionality-adhesive-functionalityis also possible.

In contrast to this, although the agents known hitherto and described atthe start exhibit a good and lasting adhesion on the sanitary object, a“sticking on” of another agent is not possible with the adhesivesanitary agents known hitherto.

Besides use in the field of toilet hygiene, the agent can also be usedas cold adhesive which, as a result of the added surfactants, can beflushed away with water. The agent can be used as cold adhesive in thesanitary sector, e.g. for the attachment of objects in urinals, but alsoin handwashing basins or on tiles in the shower, or else in kitchens,restaurants, slaughter houses or other places where water is used forrinsing.

By using the cold adhesive in places where water is used for rinsing, atthe same time as rinsing away the adhesive, cleaning also takes place asa result of the surfactants present in the adhesive.

Likewise conceivable is the use of the agent according to the inventionin washing facilities for the cleaning of motor vehicles or forapplication on/in drains or gullies, for example in order to temporarilydeodorize these.

The agent according to the invention can also be used as a wash-offpaste for accommodating bait to combat vermin or for attachment towindows or facades which are rained on, so that the agent is consumedgradually.

The individual constituents of the agent according to the invention aredescribed below:.

The adhesion promoters from the group of polystyrene derivatives arepreferably crosslinked polystyrene derivatives dissolved in mineral oil,in particular alkylene styrene copolymers, such, as, for example,hydrogenated butylene/ethylene/styrene copolymers and hydrogenatedethylene/propylene/styrene copolymers, which are available for examplefrom Penreco under the trade name Versagel M750 or Versagel M1600.

Furthermore, non-water-soluble olefin homopolymers and copolymers of twoand more olefins can be used as adhesion promoters. These compoundsinclude, for example, the polybutadiene rubbers, the styrene-butadieneblock polymers and copolymers, and the polyisopropenes. It is alsopossible to use the “random (block) polymers” which are prepared by1,3-addition of butadiene or isoprene onto styrene oralpha-methylstyrene, the homopolymers or copolymers of ethylene andpropylene, such as the ethylene-propylenediene terpolymers, naturalrubber and norbornene polymers such as polydicyclopentadiene. Thecompounds from the group of olefin homopolymers and copolymers may alsobe partially hydrogenated.

It is of course also possible to use combinations of the aforementionedadhesion promoters in the agent according to the invention.

The adhesion promoter brings about the adhesion of the agent to thesurface of the sanitary object. The agents according to the inventionadhere both to dry surfaces and also to damp surfaces.

Furthermore, the special adhesion promoters also lead to the appliedagent being sticky on its surface, such that other active ingredientagents can be stuck onto the surface of the adhesive.

In general, the adhesion promoter also forms network-like structureswhich impart the required dimensional stability to the agent even underthe effect of strong force as a result of flushing water.

The concentration of the adhesion promoter to be used is dependent onthe particular substance class and the ability of the adhesion promoterto form a network and is generally between 2% by weight and 60% byweight, preferably between 7% by weight and 50% by weight andparticularly preferably between 8% by weight and 40% by weight.

Furthermore, the agent according to the invention comprises fillers,which can be selected from the group of surfactants, thickeners,fragrances, dyes, salts, foam stabilizers, foam boosters, foamgenerators and polymeric natural substances.

In principle, surfactants which can be used are all known anionic and/orcationic and/or nonionic and/or amphoteric surfactants, preference beinggiven to pulverulent to highly pasty ones. The surfactant fraction inthe agent should be between 0% by weight and 80% by weight, preferably10% by weight to 60% by weight and particularly preferably 25% by weightto 45% by weight.

The anionic surfactants take on several tasks in the present invention;firstly, they serve, in the case of polymeric water-insoluble matrices,to emulsify the polymeric matrix without completely destroying theadhesiveness. Secondly, they make a significant contribution to theplastication of the starting polymer (adhesion promoter), by serving asviscosity increaser (thickener). Preferably, the anionic surfactantsshould also be highly-foaming in order to indicate visually a cleaningeffect e.g. in a toilet bowl. Last but not least, a good cleaning effectof the surfactants is desired which is supported by the good wettingproperties.

As anionic surfactants, preference is given to using one or moresubstances from the group of the salts of carboxylic acids, of sulfuricacid half-esters and of sulfonic acids, preferably from the group offatty acids, fatty alkylsulfuric acids and alkylarylsulphonic acids.Usually, the carbon chain distributions of the anionic surfactants arein the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22carbon atoms.

Carboxylic acids (C6-C22) in the form of their metal salts (preferablyalkali metal salts) and their natural or synthetic mixtures and alsoalkali metal salts of sulfuric acid half-esters and relativelylong-chain alcohols can likewise be used as anionic surfactants.

A further class of anionic surfactants which can be used according tothe invention are the alkali metal salts of alkyl ether sulfuric acids.Alkyl ether sulfuric acids are, like alkylsulfuric acids, synthesizedfrom fatty alcohols, which are reacted with ethylene oxide to give thefatty alcohol ethoxylates in question. Instead of ethylene oxide, it isalso possible to use propylene oxide. The subsequent sulfonationproduces the alkyl ether sulfuric acids in question.

The alkali metal salts of alkanesulfonic acids and olefinsulfonic acidscan also be used as anionic surfactants within the context of thepresent invention. Alkanesulfonic acids can contain the sulfonic acidgroup in terminally bonded form (primary alkanesulfonic acids) or alongthe carbon chain (secondary alkanesulfonic acids). Typicalrepresentatives are alkylbenzenesulfonates, particularly preferablylinear alkylbenzenesulfonates (LAS).

The aforementioned anionic surfactants can be used in their neutralizedform alone or in a mixture with one another.

According to the invention, the surfactant phase comprises, based on itsweight, preferably 10 to 90 and particularly preferably 40 to 85% byweight of lauryl sulfate.

Nonionic surfactants which can be used are alkoxylated, preferablyethoxylated, in particular primary alcohols having preferably 8 to 18carbon atoms and on average 1 to 12 mol of ethylene oxide (EO) per moleof alcohol, in which the alcohol radical may be linear or preferably2-methyl-branched or can contain linear and methyl-branched radicals ina mixture, as are usually present in oxo alcohol radicals. Inparticular, however, alcohol ethoxylates with linear radicals fromalcohols of native origin having 12 to 18 carbon atoms, e.g. fromcoconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol andon average 2 to 8 EO per mole of alcohol are preferred. In addition tothese nonionic surfactants, fatty alcohols with more than 12 EO can alsobe used. Examples thereof are tallow fatty alcohol with 14 EO, 25 EO, 30EO or 40 EO.

Nonionic surfactants which can be used are alkyl glycosides of thegeneral formula alkyl-O(G), where alkyl is a primary straight-chain ormethyl-branched, in particular 2-methyl-branched, aliphatic radicalhaving 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbolfor a glycoside unit having 5 or 6 carbon atoms, preferably glucose.

A further class of preferably used nonionic surfactants, which are usedeither as the sole nonionic surfactant or in combination with othernonionic surfactants, are alkoxylated, preferably ethoxylated orethoxylated and propoxylated fatty acid alkyl esters, preferably having1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methylesters. Nonionic surfactants of the amine oxide type, for exampleN-cocoalkyl-N,N-dimethylamine oxide andN-tallow-alkyl-N,N-dihydroxyethylamine oxide or alkanolamides can alsobe used.

The fraction of the nonionic surfactant(s) in the overall surfactantphase can be up to 50%, preferably up to 30% and particularly preferablyup to 25%.

The surfactant phase can, if desired, also be equipped with cationic oramphoteric and zwitterionic surfactants. Examples of amphotericsurfactants are fatty acid amidopropylbetaines with C5-C21 fatty acidfractions, but also amphodiacetates.

Cationic surfactants are preferably used in acidic formulations incombination with bactericidal substances. Zwitterionic surfactants canbe described by way of example as quaternary ammonium, phosphonium orsulfonium components which are joined, via an aliphatic bridge, to afurther now anionic group such as carboxy, sulfonate, sulfate, phosphateor phosphonate.

Furthermore, olefinsulfonates, ether sulfates or acid methyl tauridescan be added as foamers to the agent. If strong foamers are to be used,then preferably 1 to 50, in particular 1-25% of the surfactant phase canbe replaced by one or more foamers, e.g. from the group of betaines,alkoxylated alkyl ether sulfates or lactobionic acid derivatives. Thesefoamers can be selected from the fatty acid amidopropylbetaines with aC5-C21-fatty acid fraction such as, for example, cocoamidopropylbetaine,the alkali metal or ammonium salts of lauryl ether sulfates with 1 to 5EO, lactobionococoylamide, lactobionooleylamide, lactobionotalgamideetc. or mixture thereof. These foamers can be incorporated easily intothe pressure-sensitive adhesive. Preference is given to using thosecosurfactants which are present in solid, preferably pulverulent orhigh-viscosity form.

Besides the constituents according to the invention, the adhesive cancomprise further customary constituents, for example salts,disinfectants (e.g. oxygen or chlorine donors), preservatives, such as,for example, isothiazolone derivatives, foam stabilizers such as, forexample, alkanolamides, hydrophobicizing agents such as, for example,mineral oils or (partially) methylated siloxanes and silanes, calciumdispersants such as sodium salts of polycarboxylic acids or dyes.

By adding perfume oil or fragrances, the adhesive can also be used fordeodorizing the air.

Perfume oils and fragrances which can be used are individual odorantcompounds, e.g. the synthetic products of the aldehydes, alcohols,esters, ethers, ketones and hydrocarbons. Odorant compounds of the estertype are e.g. benzyl acetate or benzyl formate. The ethers include, forexample, benzyl ethyl ether, the aldehydes include e.g. citronellal, theketones include α-isomethylionone, the alcohols include citronellol,eugenol, geraniol and linalool. The hydrocarbons include primarily theterpenes such as limonene and pinene. However, preference is given tousing mixtures of different fragrances which together produce thedesired scent note. These also include those perfume oils which comprisenatural odorant mixtures, as are accessible from vegetable sources, suchas e.g. pine oil, citrus oil, lavender oil, mint oil or oil from orangepeel.

The fragrances are incorporated directly into the batch inconcentrations between 0.25% by weight and 20%, preferably between 3% byweight and 15% by weight and particularly preferably between 5% byweight and 10% by weight.

If desired, salts such as, for example, sodium sulfate can also be addedto the formulation as fillers, for example in order to increase thedissolution rate. In the case of particularly cost-effective product,the salt fraction can be up to 90% by weight. In general, the saltfraction is up to 10% by weight, preferably up to 5% by weight. Suitablesalts are alkali metal salts of strong acids, such as sodium sulfate,sodium chloride or else sodium polyphosphate. It is likewise possible touse the alkali metal salts of the mono-, di- and polycarboxylic acids,but also alkaline earth metal salts of strong acids, such as calciumsulfate or salts of carbonic acid.

In order to increase the ability to be flushed away, calcium soapdispersants, such as e.g. ampho-dipropionates (Lonza KL grade) or maleicacid/acrylic acid copolymer Na salts (BASF Sokalan grades such asSokalan CP5 or CP45) can be added to the agent.

Moreover, all dyes which do not have marked substantivity towards thesurfaces to be treated with the dye-containing agents can beincorporated as fillers into the agent. If water-soluble dyes are usedin the formulation and the latter then comes into contact with water asa finished product, e.g. upon flushing with water in a toilet bowl,interesting color progressions can be achieved which can also becorrelated with marketing arguments. For example, a slow blue coloration(from pale blue to deep blue) can indicate the slow activation of anactive ingredient up to its maximum activity.

Similarly, the adhesive can also be rendered acidic and comprise, forexample, substances which dissolve lime scale or urine scale (acids) asfillers.

Furthermore, (co)thickeners can be added to the agent according to theinvention in order to increase the plasticity of the agent.(Co)thickeners which can be used are, for example, bentonites, powdersurfactants, xanthans, polybutadiene rubbers, polyisopropenes, blockcopolymers, which contain linked oligomers consisting of oligo- orpolyethylene oxide and/or oligo- or propylene oxide and/or oligo- orpolybutylene oxide, and also aryl ethoxylates or alkyl-aryl ethoxylates.The polymeric natural substances such as the lignins or their alkalimetal or alkaline earth metal salts can also be used as (co)thickeners.

One preferred group of (co)thickeners is the hydrophilic xanthans.Through their use, a very hydrophilic compound is introduced into theagent which, upon sticking the agent onto a damp surface, immediately“sucks up” the water.

Furthermore, hydrophobicizing agents such as, for example, Aerosil, inparticular thoroughly methylated Aerosil (Carbot Carbon) can be added asfillers to the adhesive.

If an increase in the rate of adhesion should be desired, so-calledtackifiers, in particular from the class of hydrocarbon resins, naturalresins such as tall resin or balsam resin, or polyterpene resins, canalso be added as fillers to the agent.

In order to counteract unpleasant odors, the adhesive can also comprisemalodor counteractants, which are preferably added to the fragrances.Such malodor counteractants are described, for example, in U.S. Pat. No.7,288,507 B2.

The adhesive according to the invention can be applied and replaced in ahygienic manner without touching possibly contaminated devices attachedto the WC bowl.

An essential advantage of the agent according to the invention is thatit can be portioned as the consumer desires and/or can be supplied indifferent portion packs. The adhesive can be applied for example bymeans of an application syringe or by application of preportionedamounts by means of suitable devices. These application devices may befor example “clip systems”, grippers or small plates removable fromfilms, dispenser systems with pretensioned elements which fire acorresponding portion e.g. onto a ceramic surface.

The agent according to the invention can also be applied in a simplemanner at the same time to different places on the sanitary object, forexample in order to stick on two or more active ingredients which, indirect vicinity, would adversely affect one another in their effect,such as, for example, a deodorizing tablet and a bleaching tablet.

The achieved adhesion to the sanitary object, even in the case ofapplication to a vertical surface, is so good that the agent does notcome off even under the additional action of force of streams of flushwater.

The adhesives according to the invention can only be flushed away aftera relatively large number of flushing operations. The number of flushingoperations is naturally governed by the composition of the particularagent, the amount applied and the geometry of the applied agent and isgenerally, for an application with a thickness of 2 to 5 mm, between 50and 150, in particular more than 120, flushes.

If the agent is used as adhesive in the toilet bowl, the durability isessentially defined via the flush-away time of the applied further body(bar-shaped agent). In the case of a conventional toilet block, thus aservice time of from 100 to 200, in many cases >250 flushes, can beachieved, the adhesive agent being gradually washed away together withthe stuck-on material. The applied amount is 3 to 15% by weight, inparticular 5 to 10% by weight, of the mass of the stuck-on agent.

Preferably, the agent according to the invention is white,ointment-like, pasty and/or cream-like and dimensionally stable so thatit does not “run off” or “drip”.

The adhesion and also the shape of the agents is retained despite theconsiderable forces (friction, deformation, shear effect) which act as aresult of the water flushing.

The agent essentially exhibits pseudoplasticity, i.e. the viscositydecreases with increasing shear forces. If the shear rates are low,however, a severe flow constraint is observed; moreover, the viscositycurves at a shear rate ramp between 2.5 s⁻¹ and 30 s⁻¹ show theappearance of local maxima. There are evidently areas of differingviscosity or the agent changes its structure over the short measurementtime (ramp time 100 sec).

The viscosities of these agents, to be determined using a Haakeviscometer, plate/plate system, plate diameter. 10 mm at a sheargradient of 2.62 s⁻¹ and 20° C., should be at least 30 Pas, preferablyat least 45 and particularly preferably at least 100 Pas. Preferably,the viscosities should be between 150 or 300 and 6000 Pas andparticularly preferably between 200 and 1000 or between 1000 and 4000Pas.

Preferably, the agents according to the invention which comprisesurfactants produce a finely-bubbled foam which can be adjusted inrespect of its volume by suitable additives (foam boosters). The foamnumbers of the agents according to the invention should be more than 40ml of foam. Particular preference is given to agents with foam numbersof >60 ml, very particular preference being given to foam numbers of 140ml or even more than 200 ml.

The surface tension of the agents can be between 50 and 65 mN/m.Preference is given to those agents whose surface tension is <60 mN/m.Particular preference is given to agents which achieve surface tensionsequal to or less than 40 mN/m. The surface tension is a measure of thewetting of the surface. The lower the surface tension, the better thesurface is wetted. A good wetting effect is a prerequisite for a goodcleaning performance of the agents under consideration.

The agent according to the invention is prepared by stirring thecomponents together at room temperature.

The invention is described below by reference to various embodiments andexperiments.

Table 1, which is attached at the end of the description, lists variousformulations of the adhesives according to the invention.

The flush numbers in table 1 were determined on applied amounts of 2-5g.

Table 2, which again is attached at the end of the description, liststhe starting materials used for producing the agents according to theinvention in table 1.

The adhesives of the invention according to formulations V18 and V24exhibit strong adhesion and are so sticky on their outside thatconventional toilet cleaning agents with a mass of up to 50 g can bestuck onto the agents depending on what amounts of adhesive are applied.The ratio of stuck-on mass of the bar-shaped agents to the adhesive masshere is at most 100:1, preferably at most 50:1 and particularlypreferably at most 10:1. Better adhesion of the agent is naturallyachieved if the adhesive surface is larger. The customary adhesivesurfaces are between 1000 mm² and 800 mm² (full-area contact). However,they may also be less than 400 mm² if the adhesive is applied in theform of circular beads.

In all of the flushed-off experiments, the surfactants used were anionicsurfactants. The flush numbers of these agents exhibit relatively highto high service lives.

Formulation V24 comprises only one (anionic) surfactant and an adhesionpromoter. This agent consisting only of two components also exhibits thedesired adhesion, the required stickiness and flush numbers of more than100.

The pure adhesion promoter Versagel M1600 (hydrogenatedbutylene/ethylene/styrene copolymer) applied to the toilet bowl, bycontrast, adheres firmly in the bowl and cannot be flushed away at alleven after a large number of flush cycles. Toilet blocks can also bestuck onto these adhesion promoters, although the toilet blocksgradually migrate downwards with the adhesive Versagel.

Table 3 shows that the agents according to the invention differsignificantly from the agents known hitherto from EP 1325103 B1.

To determine the foam numbers, 100 ml of the stock solution thermostatedat 20° C. are transferred to a 250 ml mixing cylinder, which is closedwith a PTFE stopper. The cylinder is then moved to and fro twenty times(inverted 20 times). After in each case 30 sec/5 min/30 min, thegenerated foam volume (ml) is read off and noted.

All of the investigated agents according to the invention adhere/stickexceptionally both to dry and to wet surfaces.

Also, they are so sticky on their outside that conventional toiletcleaning agents with a mass of up to 50 g or even more can be stuck ontothe agents, depending on what amounts of adhesive are applied. In all ofthe flushed-off experiments, the surfactants used were anionicsurfactants. The flush numbers of these agents exhibit relatively highto high service lives.

TABLE 1 V18 V24 in g in g Tensopol USP 49.6 70.0 surfactant 94 Versagel36.7 30.0 adhesion M1600 promoter Kelzan ASX 0.99 thickener Orange Fun12.71 perfume Total [in g] 100.00 100 Flushes: >150 130

TABLE 2 Manufacturer Grade Chemistry Function Tensopol USP 94 ManroTensopol USP 94 C12-C16 lauryl sulfate surfactant Orange Fun Quest #F561415 perfume Kelzan ASX Kelco Kelzan ASX XanthanThickener/cothickener Versagel sblack/Penreco M1600 Mineral oil (and)adhesion promoter M1600 hydrogenated butylene/- ethylene/styrenecopolymer (and) hydrogenated ethylene/- propylene/styrene copolymer

TABLE 3 Foam number [Pas], PP, 10 mm, [Pas], Senior PK 5, Experimentnumber [mm] 20° C., γ′ = 2.62 s⁻ 20° C., ¹γ′ = 0.3 s⁻¹ Surface tension18 n.d. 328 not measurable n.d. Comparison gel from 70/25/10 524 n.d.56.6/48.7/45.5 EP 1325103 B1

1. An agent for the sanitary sector, which agent can be applied directlyon the sanitary object, adheres there and can be flushed away only aftera relatively large number of flushing operations, where the agentcomprises fillers from the group of surfactants and also an adhesionpromoter, characterized in that the adhesion promoter is selected fromthe group of hydrogenated polystyrene derivatives and olefinhomopolymers and copolymers of two or more olefins, where the olefinhomopolymers and copolymers may also be partially hydrogenated, and theviscosity of the agent is at least 30 Pas, measured using a Haakeviscometer, plate/plate system, plate diameter 10 mm, at a sheargradient of 2.62 s⁻¹ and 20° C. and the agent is so sticky that it canserve to attach bar-shaped agents in the toilet bowl, wherein theconcentration of the surfactants in the case of an adhesion promoterfrom the group of polyalkyleneimines is between 7 and 60% by weight. 2.The agent as claimed in claim 1, characterized in that the adhesionpromoters from the group of polystyrene derivatives are crosslinkedpolystyrene derivatives dissolved in mineral oil, preferably alkylenestyrene copolymers, in particular from the group of hydrogenatedbutylene/ethylene/styrene copolymers and hydrogenatedethylene/propylene/styrene copolymers.
 3. The agent as claimed in claim1, characterized in that the adhesion promoter from the group ofnon-water-soluble olefin homopolymers and the copolymers from two ormore olefins are selected from the group of polybutadiene rubbers,styrene-butadiene block polymers and copolymers, polyisoprenes, random(block) polymers which are prepared by 1,3-addition of butadiene orisoprene onto styrene or alpha-methylstyrene, homopolymers or copolymersof ethylene and propylene, such as ethylene-propylenediene terpolymers,ethylene-ethylene oxide copolymers, natural rubber and norbornenepolymers such as polydicyclopentadiene.
 4. The agent as claimed in claim1, characterized in that the concentration of the adhesion promoter inthe agent is between 2% by weight and 60% by weight, preferably between7 and 50% by weight and particularly preferably between 8% by weight and40% by weight.
 5. The agent as claimed in one of claims 1 to 3,characterized in that the concentration of the adhesion promoter in theagent is between 15% by weight and 80% by weight, preferably between 20and 70% by weight and particularly preferably between 30% by weight and50% by weight.
 6. The agent as claimed in one of the preceding claims,characterized in that the fillers are selected from the group ofthickeners, fragrances, dyes, salts, foam stabilizers, foam boosters,foam generators and polymeric natural substances.
 7. The agent asclaimed in claim 6, characterized in that the surfactant fraction in theagent is between 0 and 80% by weight, preferably 10 to 60% by weight andparticularly preferably 25 to 45% by weight.
 8. The agent as claimed inone of claims 6 and 7, characterized in that the surfactants arepulverulent or highly pasty.
 9. The agent as claimed in one of claims 1to 8, characterized in that the surfactants are anionic surfactants andare selected from the group of salts of carboxylic acids, sulfuric acidhalf-esters, sulfonic acids, relatively long-chain alcohols and fattyalcohol ethoxides.
 10. The agent as claimed in one of claims 6 to 9,characterized in that the surfactants are nonionic surfactants and areselected from the group of alcohol ethoxylates, alkyl glycosides,alkoxylated fatty acid alkyl esters, amine oxides and alkanolamides. 11.The agent as claimed in claim 6, characterized in that the agentcomprises fragrances or perfume oils in a concentrations between 0.25%by weight and 20% by weight, preferably between 3% by weight and 15% byweight and particularly preferably between 5% by weight and 10% byweight.
 12. The agent as claimed in claim 6, characterized in that theagent comprises up to 90% by weight of salts, in particular up to 10% byweight, preferably up to 5% by weight, of salts, preferably from thegroup of alkali metal and alkaline earth metal salts of strong acids orof mono-, di- and polycarboxylic acids.
 13. The agent as claimed inclaim 6, characterized in that the agent comprises (co)thickeners fromthe group of bentonites, powder surfactants, xanthans, polybutadienerubbers, polyisopropenes, block copolymers, aryl ethoxylates oralkyl-aryl ethoxylates or polymeric natural substances.
 14. The agent asclaimed in one of the preceding claims, characterized in that the agentis a water-soluble and/or water-dispersible temporarily adheringadhesive.
 15. The use of an agent as claimed in one of the precedingclaims, characterized in that the bar-shaped compositions that can bestuck on are conventional rim blocks with one or more phases, rim blockswith scented phase, rim blocks containing bleach, compacted tablets,water-soluble or water-insoluble plastics comprising active ingredients,deodorization tablets, solid deodorization gels, bleaching tablets,descaling tablets or intensive cleaning tablets.
 16. The agent asclaimed in one of the preceding claims, characterized in that the agentcomprises cleaning and/or deodorization and/or bleaching and/or coloringadditives.
 17. The agent as claimed in one of the preceding claims,characterized in that the agent is ointment-like, pasty and/orcream-like and dimensionally stable.
 18. The agent as claimed in one ofthe preceding claims, characterized in that the surface tension of theagent is between 50 and 65 mN/m, in particular below 60 mN/m.
 19. Atoilet cleaning set comprising at least one agent as claimed in one ofthe preceding claims and one or more bar-shaped compositions from thegroup of rim blocks having one or more phases, rim blocks with scentedphase, rim blocks containing bleach, compacted tablets, water-soluble orwater-insoluble plastics comprising active ingredients, deodorizationtablets, solid deodorization gels, bleaching tablets, descaling tabletsor intensive cleaning tablets.
 20. The use of an agent as claimed in oneof the preceding claims as cold adhesive in the sanitary sector, inparticular for attaching objects in urinals, handwashing basins ortiles, or in kitchens, restaurants, slaughter houses, washing facilitiesor for application on/in drains or gullies or as paste for accommodatingbait to combat vermin or for attaching to windows or facades.
 21. Theuse as claimed in claim 20, characterized in that the mass of the agentapplied to the object is 3 to 15% by weight of the mass of the object.22. A method for producing an agent as claimed in one of the precedingclaims, characterized in that the individual components are stirredtogether at room temperature.